Process of producing pulp



Patented June is, 1929 UNITED STATES PATENT. ,OFFICE."

ROBERT A. MARR, NORFOLK, VIRGINIA.

rnocnss or PRODUCING Petr.

. 3 v No Drawing. Application filed March 28, 1924, Serial No. 702,688. Renewed. March 15, 1929.

In my copending application 407,7 59, filed September 2, 1920, I have described a process of producing pulp from ,various woods, including porous woods, non-porous woods,

5 and other vegetable growths such as banana stalk, sedges, swamp grass, bear grass, salt marsh grasses, cocoanut husks, straw and the like, the aid process consisting in boiling the Wood or other material with a solution of' i-ron'sulfate, copper sulfate or various other sulfates, the boiling being continued until the cementitious matter in the wood has been rendered readily friable, but not until the same has been dissolved. After this the treated vegetable material is removed from the cooking liquor and is reduced to a pulp, in the presence of water, and the pulp can then be worked up into finished products in the well known manner. Y i i In a later copending application 595,215,

filed October 17, 1922, reference is made particularly to'the use of sulfates of the alkaliforming metals, particularly sodium sulfate, potassium sulfate,magnesiui sulfate, and 5 special reference being made therein to the use of cane,.although it is to be understood that the process is also applicable to the treatment of woods as above referred to and other forms of vegetable growth.

In another copending application 616,609, filed February 2, 1923, I- have also referred tothe use of sodium sulfate, magnesium sulfate aluminum sulfate and other sulfates,

for the production of pulp and fiber products, from all kinds of vegetable material.

In another copending application 616,610, filed February 2, 1923, I have referred particularly to the use ofkainit, as the chemical to be used in reducing vegetable growth in accordance with the procedure above described. p

I have. now found that various other salts can be used in a somewhat similar manner, and particularly the salts of the alkali-forining metals, sodium, potassium, magnesium and the like, those salts which do not have any reducing e. deoxidizinglaction being found to be particularly suitable, and of such saltsl mention, sodium nitrate and 5 especially sodium chloride. It will be understood that the nitrates arid chlorides of the other alkali-forming metals can also be used. For commercialreasons, sodium chloride is preferred, this being an extremely cheap substance, available" everywhere, and

I call attention to the fact that the salt used 9 ural state or reinforced with a small ;additional amount of common salt can be employed.

In this connection it may be called to at tention that sea water'which may be considered as a solution of highly impure sodium, chlorid, is farbetter, for the cooking operation, than a solution of table salt. Ordinary sea water contains about 3% of actual sodium chlorid together with smaller amounts of chlorids and sul-. fates of magnesium, potassium and calcium, these impurities amounting to about one fourth as much as the content of sodium chlorid. Hereinafter, the term sodium. chlorid will be used in its chemical sense and the term common salt used to designate a'more or less impure article, and the 30 term sea salt is used to designate mixtures containing some at least of the common impurities of seawater. l d

When using common salt and sea salt, it is of importance that the strength of the solution should be properly maintained, and I find that'solutions between 3 and 3 5% V strength seem to give the best results, although solutions between 2% and 5%,can be satisfactorily employed.

The length of time of the cooking operation and the temperature of the cooking operation are also of very substantial importance. The temperature is easily controlled by controlling the pressure and most satisfactory results are secured when the pressure I is maintained at between about 80 and lbs, per square inch, this amount of pressure being maintained for, about 1 to 3 hours. The temperature should preferably not be 0 purified salt, such as 70 allowed to go up to a temperature corresponding to a pressure of 120 lbs., at any time, during the cooking, and in any event should not be allowed to go substantially above this point as the material is liable to become injured.

In a preferred form of execution of the i process, the wood or other material to be is allowed to soak for awhile,

digested, is placed in a digester, which may be made of cast iron or steel, and which does not require any lining of tile, bricks or similar material, and the wood can, if desired, be enclosed in a cage made of coarse wire sc'reening or equivalent material. The wood can if desired, be in the form of chips, such as are commonly used inmaking pulp, although if desired, very much larger chips can be satisfactorily used. Very satisfying results have been secured when using pieces of wood, say about 3 inches long (in the direction of the grain, and half inch or up to, an inch square). Other sizes can of course be employed. The digester having been filled with the wood or other material, a solution of common salt, say containing about 3 to 3 strength is then run in, the

digester closed and the material is then heated, for instance by'blowing in superheated steam, until the pressure is raised to about 80 or 85 lbs., per square inch, which pressure is maintained for about-say 3 to 4 hours, after which the solution is blown oif and the treated wood removed from the diester, and placed in cold water, in which it say for one to two hours or more; The pieces may, if desired, be then run through a splitting ma- I, beating operation,

the form of a fine powder. can again be put backinto the beater, and

chine and are then run between heavy rollers or are mashed up in a mill such'as an edge runner, "and the material then run through an ordinary pulper, with water, and then run 'into a beater. The heating operation may be started with the roll raised, say five or six turns above the bed, and the roll can be gradually or rapidly lowered during the say down to about three or four turns above the bed. This beating operation does not have to be continued for a very long period,a 5eat ifig for only fifteen or twenty minutes gives very satisfactory results". After this beating, the material can if desired be subjected to a light wash, to remove a substantial part of the cementitious matter, which has now been broken up into The material beaten for say another half hour, more or less, after which the material can be run onto a paper machine, or if desired, before being run onto the papermachine, any desired amount of sizing and size precipitant (such ;pressure gage of the asrosin size and aluminum sulfate) can be added.

If the pressure in the cooking operation is maintained somewhat higher, say up to 100 chloride,

or 110 lbs., per square'inlch, the time of cookmg can be substantially reduced, thus I find that a pressure of 110 lbs., maintaine d for about 1% hours to 2 hours gives very satisfactory results.

In most cases it is advisable to also add small amounts of sulphate or other salt, in-

cluding those above referred to, to the cook cooking operation the liquor acquires a somewhat yellowish color and an odor resembling caramel or burnt sugan The strength of the solution and the time of cooking should be regulated so as to produce this caramel odor, as otherwise the results will be far less satisfactory. s i

The sheeted product produced by this process, will be of a bufi to brownish color, depending upon the particular wood,being treated, or other material being treated. Spruce and similar woods are found to produce a light buff paper very suitable for wrapping paper, and having. a very high strength, resembling kraft paper. I call at-- tention to the fact that even with the very small amount of beating above referred'to the product is free from shives, and particularly after a small amount of size and alum efficiency, and it is desirable,

has been added, the material works very free on the screens of the paper machine.

The followingexamples are given, showing procedure falling within the scope of the present inventiombut it is to be understood trative and not a restrictive sense.

Example 1.-A solution of salt was prepared, containing about 3.5% of sodium and small amountscof the other salts above referred to, the said solution being prepared by adding a small amount of ordinary table salt, to sea water. Large chips of Adirondack spruce, yellow poplar, and also spruce in the form of standard chips (the latter containing about 40% of moisture) and the large spruce chips being in a substantially air-dry state, were placed in the digester and the above solution was then run in to completely cover the same.

The temperature was then raised (by external heating) until a pressure of about 110 lbs, per square inch,

digester. This pressure was maintained for about 1% hours, at which time the heatwas shut off, the digester allowed to cool somewhat, and the was registered on the.

from the solution and minutes, and a port on to be of the beaten and washed materials, a little "'then run through a beater, in which cage carrying the wood was then removed placed in a tank of water, in which it was left over night. The following day, portions of each of the materials above.v referred to, were first crushed a pulper and then run into 4 the beating was conducted with the roll raised about five turns above was Continued in each case, for forty-five portion of each material was then slieeted. Extremely strong sheets were thereby produced. Another portion of each pulp was thenfgivena light wash, and a thereof was sheeted. The sheeted materials'so formed, in each case, was found a high strength, and very suitable as a wrapping paper. i

rosin size and alum were added, and the ating ,continued' for another fifteen minutes. Th'esematerials were then made into sheets of paper, which were found in all cases to possess good strength and appearance! be of wet spruce, a light bufl color.

Emample 2.The solution remaining from the first cook, was then useglfor cookingcane, including bamboo and Machrosperma 'tecta, some of the bane. was in a dried sta;te,

were found to and some was in a greenstate 'The pressure was raised to 110 lbs., by heating, and.

1 this amount of pressure was maintained for "overnight. The through rollers,

about an hour. At,the end of this time and after cooling somewhat, the cooked material.

was removed from the digester and thrown into a tank of water, and allowed to stand,

following day this-was run was then run,',with Water, through a pulper, and then into-a beater; in which it was beaten half an hour with the rpll raise four turns. A portion of the material was then removed from the beater, and

was made into a ,sheet. This gave a strong sheet of a brownish color. Another portion of the same was given a light wash, and was made into a sheet, of a light brown color,

placed in a solution Bfound advisable to say half, of the ccinentitiousmatter, and 110 mal concentration strength, and the material was-digested, for

1 hoursat a pressure of about 1-10 lbs. per I square inch. The total time that the inate- Q rial was at a to 2 hours.

During this run the pressure was allowed to go up to 120 lbs, 'for a short material was then worked up as above indipressure above 90 lbs, amounted the first two examples, probably on account of the fact that the pressure in the digester in the cooking operation, was allowed to run up to 120 lbs.

I call attention to the fact that it is advisable to soak material in cold water for several hours in,order to becomethoroughly water soaked before proceeding to the C1 ing operation.

dried, then soaked in water for one or several days, in order to become thoroughly wetted before being crushed. This latter procedure might be advisable in cases where the cooking is. to be conducted in one plant and the subplant. I also or dry "laps, Which can be shipped to paper product mills located at another place, for being converted into the final product.

latter is preferable, instead of drying the cooked materiah ,1 have above referred to making paper from the pulp produced, and in this operation it is sometimes advisableto wash out a large proportion of-the cementitious matter,

which has been converted into apulverulent state, It is,not necessary, do this, and in some instances, it may be wash out a' small part,

this ceinentitious matter so washed out can bejcollected as a by-product and worked up into various plastic objects or molded articles.

EwmmpZe.4..'White birch in tlie form 0%,

half-inch boards, red birch in the form of 1 inch boards, sawed 1 incheslong, Glens Falls maple, 1 x 1 x 3 inches, pieces ,ot' yellowpoplar about 9 x1 x 2 inches, black gum slabs, dry white poplar, dry maple slabs, largef dryl spruce chips about X x 3 inches,- green cane in 8 inch lengths, green pine'and dry pine, constituted the raw material used inth'is run. The materials were placedinto a coarse wire mesh basket and lowered into a vertical digester, and ocean water of norcover the cage of -material.

About a gallon of the sea 'waterrfwas used fer. each two during the crushing and beating steps. however, in all cases to. 7

was addedto completely -wet spruce-chips, Q

. part was sized. with a pounds of wood, etc. The digester was then closed and heat applied at thebottom. The pressure was run up to 110 lbs.,w as held'at that point for about 1 hours, the heat shut off and the digester and Contents allowed to cool for an hour, the digester was opened'and the cage, of chips was removed to atank of fresh cold water, and allowed to soak for an hour or so.

Thelarge chips were split (lengthwise of the grain) into pieces about half inch square, and samples of each of the materials were then crushed, run through a pulper with water, and the pulp beaten with-the roll 6 turns up at the beginning and quickly run down one or two turns, the beating was first continued 15 minutes, half of the pulp.withdrawn, part of which was given a light wash and sheeted and anotherpart directly sheeted. he remainder (not withdrawn from the beater) wasbeaten another half hour, a part withdrawn and sheeted, another solution of rosin soap containing a little rubber latex, followed by a small amount of 'aluminum sulfate solution, and then sheeted.

All of the products were of very excellent quality.

Example 5.Commercial calcium chlorid in the form of a solution of 2 4% strength.

- Wood used was white birch, oak, white poplar, hickory, black gum and spruce, partly I Wet and partly dry, and cane. The spruce was in the form of standard size chips, and the,.other woods in the form of large chips about. four inches long, in the direction of the grain, and averaging about half inch square. The cane was cut in lengths of about six inches, part of this was green and partof it was dry. Each kind of wood, etc, was bundled separately, and all put into a wire mesh basket." The calcium chlorid solution was added, to completely submerge the basket containing the material, and the 1 lid of the digester closed and bolted down.

Heat was applied untilthe pressure gauge registered 110 lbs., which was continued about one hour, the heat turned off and the material allowed to cool for two hours in the liquor. The basket "of cooked material was then transferred to cold water, after soaking an hour or more was crushed,

' pulped, beaten and .sheeted'as in the above examples.

Excellent products were produced.

In some cases it is advisable to employ somewhat stronger or Weaker solutions of calcium chlorid, say from about 2 to 4% or even slightly stronger.,

In place of using sea salt alone, it is advisable in some cases to use a mixture of this with calcium chlorid, maghesium chlorid. In other cases it is sometimes advisable to add sodium sulfate, magnesium sul fate, alum or other sulfates. These add i and ori'gi a1 tions may amount to,

say'5 to 10% or even more, of the solids content of the sea water.

' In connection with the operation of crushing the digested anaterial, before pulping, this step is usually advisable. The chips can be run directly (preferably after soaking in water for a few into the pulper or beater (the roll of the latter being preferably raised somewhat more than above indicated) but it is usually more economical to first crush, e. g. in an edge runner, then run with water through the pulper. This crushing and pulping act to shred the material to a considerable extent, and are not. to be confused with such an operation as mechanical wood grinding, which latter tears and breaks up the fibres to produce only very'short fibred pulp.

In the cooking'operation, it is to be understood that the cooking proceeds clear to hdurs) from the digester like material and it is,regarded as astonishing that such a result can be secured in a short time, such as one hour as mentioned in some of the above examples, and particularly at 'the low pressures used in this process.

In cooking with common salt and sea salt it is quite essentialthat the strength of the "solution be kept withih or substantially within the limits above indicated.

The use of sea Water is of course advisable, When mills are to be located close to the salt water, and if desired, sea water can be used for the pulping and for a portion of the Washing operation, as well as 'for the cooking step. It is however, advisable in some cases to use fresh Water for the final washing; in order: to remove at least a major part of the salt from the final product.

IVhile I have above referred to making paper from this product, it will be obvious ;that the same can be used for making various other pulp objects, including card-board heretofore largely used in this country for the production of paper pulp, from wood and similar. materials. In cases Where the cefinentitious matter is not washed out. I am' able .to produce, in the form.o'f finished pulp, about '90 to 95% of the dry weight of the wood or similar material under treat- 'Also I call attention to the. short time I ing somewhat of digestion and the short time of the beat-' ing operation.

The wood or other material to be treated in accordance with thepresent process can I 5 be either in a dry state or a green state, or it may be saturated with water, as in the case of logs which have been floated from the forest to the mill Wood which is in a green state is apparently capable of producstron'ger pulp, than Wood which has been thoroughly dried.

I claim: P 1. A process of producing pulp which comprises subjecting a cellulosic material to a partial cooking treatment, by digesting the same in a l to 5% solution of a normal salt I of an alkali-forming-metal,such salt being derived from an acid which is stable at the temperature of the digesting operation, contlnuing this treatment until the cementitious matter is rendered readily friable, but notr until the" said material has been" reduced to a pulp, the digestion being at a temperature siiflicient to produce a caramel odor in the liquid, and-thereafter reducing the material to a pulp by mechanical treatment.

2. A process of producingpulp which comprises subjectinga cellulosic material to a partial cooking treatment, by digesting the same in a 1 to 5% solution of a normal salt of analkali forming-metal, such salt being derived from an acid which is stable at the temperature of the digesting operation, such salt being substantially without oxidizing or deoxridizlng properties, continuing this treat mentuntil the cementitious matter is rendered readily friable, but not until the said material hasbeen reduced to a pulp, the diges tion being at a temperature sufficient to produce a'caraniel odor in the liquid, and thereafter reducing the material to a pulp'by mechanical treatment. A w

3. A process of producing pulp which comprises subjecting, a cellulosic material to a partial cooking treatment, by digesting the same in a 1 to 5% solution of a halide of an alkali-forming meta-l, continuing this treatment until the cementitiousimatter is rendered readily friable, but not until the said material has been reduced to a pulp,

the digestion being at a temperature sulficient to produce a carame and thereafter reducing the material to a pulp by mechanical treatment.

4. A process of producing pulp which comprises subjecting a cellulosic material to a partial cooking treatment, by digesting the same in a 1 to 5% solution of a chlorid' of an alkali-forming metal, continuing this treatment until the cementitious matter is rendered friable, but not until the said material has been reduced to a pulp, the digestion being at a temperature suflioient to produce a caramel odor in the liquid, and there 1 Odor in i after reducing the material to a pulp by mechanical treatment.

v 5. A process of producing pulp which comprises subjecting a cellulosic material to a partial cooking treatment, by digesting the same in a 1 to 5% solution of sodium chlorid, continuing this treatment until the cementitious matter is rendered readily fri-- able, but not until the said material has been reduced to a pulp, the digestion being" at a temperature sufficient to produce a caramel odor inthe liquid, and thereafter reducing thev material to a pulp by mechanical treatment.

6. A process of producing pulp which comprises subjecting a cellulosic material to a partial cooking treatment, by digesting the'same in a 3 to 3;5%solution of a 'normal salt of an alkali-forming metal, suchsalt being derived from an acid which is stable at the temperature of the digesting operation, continuing this treatment until the cementitious matte-r is rendered readily friable, but not until the said material has been reduced to a pulp, the digestion being at a temperature suflicient to produce a caramel odor in the liquid, and thereafter reducing the material to a pulp by mechanical treatment. 1

- 7. A process which comprises boilingcellulosic and ligneous material in solution of common salt, at about 8 0 to 100 lb. pressure,

soaking the product in cool water and thereafter mechanically reducing the same to pulp. v

8. A process of producing .pulp which comprises subjecting a cellulosic material to a partial cooking treatment, by digesting the same in a solution ofia normal salt of an alkali-forming metal, such salt being derived from an acid which is stable at the temperature of the digesting operation, contiu'uing this treatment until the cementitious matter is rendered readily friable, but not until the said materials has been reduced a pulp, the digestionbeing at,a temperature sufficient to p'roducea caramel odor in the liquid, and under'a pressure of about 80 to 120' lbs, soaking the cooked material in cool water, and thereafter reducing the material tcra pulp by mechanical treatment.

9. A process 'which comprises cooking woody material in a solution containing about 1 to 5% 'of common salt and smaller zhnoimts of chlorids or sulfates of bivalent alkaline earth metals, until the cementitious matter is rendered friable, but not long enough to reduce the material to a pulp, soaking the cooked product in water, and

mechanically reducing thesame to-a pulp.-

10. A process which comprises cooking woodyunaterial in a solution containing about I to 5% of common salt and smaller mounts of salts of metals of the second group of the periodic classnication, until the about 1 to 5% of common salt and also concementitious matter is rendered friable, but taihing metal sulfates, until the cementitious. 1

not long enough to reduce the material to matter is rendered friable, but not long a' pulp, soaking the eookedlprocluct in water, enough to reduce the material to a" pulp, 5 and mechanically reducing the sameto a.- soaking the cooked product in water, and pulp. y mechanically reducing the same to e, pulp. 11. A process which comprises cooking In testimony whereof I affix my signature. woody material in a solution containing v v IROBERT A. MARE. 

